High-K metal gate process and device

ABSTRACT

An embodiment is a method of semiconductor processing. The method includes depositing a high-k gate dielectric layer over a semiconductor fin. A barrier layer is deposited over the high-k gate dielectric layer. A silicon passivation layer is deposited over the barrier layer. A nitrogen treatment is performed on the silicon passivation layer. A capping layer is deposited over the silicon passivation layer. The capping layer is annealed.

BACKGROUND

The semiconductor integrated circuit (IC) industry has experienced rapidgrowth. In the course of the IC evolution, functional density (definedas the number of interconnected devices per chip area) has generallyincreased while geometry size (i.e., the smallest component (or line)that can be created using a fabrication process) has decreased. Ascaling down process generally provides benefits by increasingproduction efficiency and lowering associated costs. Such scaling downhas increased the complexity of processing and manufacturing ICs. Forthese advances to be realized, similar developments in IC manufacturingare needed.

As the semiconductor IC industry has progressed into nanometertechnology process nodes in pursuit of higher device density, higherperformance, and lower costs, challenges from both fabrication anddesign have resulted in the development of three-dimensional (3D)devices, such as fin field effect transistors (FinFETs). Advantages ofFinFET devices include reducing the short channel effect and increasingthe current flow. There has been a desire to use a FinFET device with ahigh-k gate dielectric and a metal gate electrode to improve deviceperformance as feature sizes continue to decrease.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 is a flow diagram illustrating a process of manufacturing asemiconductor device in accordance with some embodiments.

FIG. 2 is a schematic perspective view of a semiconductor substrate atone stage of manufacturing a semiconductor device with a dummy gatestructure in accordance with some embodiments.

FIGS. 3-15 are schematic cross-section views of a semiconductorsubstrate at various stages of manufacturing a high-k metal gatestructure in accordance with some embodiments.

FIG. 16 is a graph of an atomic percent content in a high-k metal gatestructure in accordance with some embodiments.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

High-k metal gate structures, including a high-k dielectric layer and ametal gate, are used to increase circuit performance. Some embodimentsare described in the context of a replacement gate process.Implementations of some aspects may be used in other processes. Forexample, other example processes can include a gate-first process.

Some embodiments are described in the context of FinFETs. The fins ofFinFETs may be patterned by any suitable method. For example, the finsmay be patterned using one or more photolithography processes, includingdouble-patterning or multi-patterning processes. Generally,double-patterning or multi-patterning processes combine photolithographyand self-aligned processes, allowing patterns to be created that have,for example, pitches smaller than what is otherwise obtainable using asingle, direct photolithography process. For example, in one embodiment,a sacrificial layer is formed over a substrate and patterned using aphotolithography process. Spacers are formed alongside the patternedsacrificial layer using a self-aligned process. The sacrificial layer isthen removed, and the remaining spacers may then be used to pattern thefins. Implementations of some aspects may be used in other devices. Forexample, other devices include Horizontal Gate All Around (HGAA) FETs,Vertical Gate All Around (VGAA) FETs, nanowire channel FETs, and otherdevices.

Some variations of the example processes, structures, and devices aredescribed. A person having ordinary skill in the art will readilyunderstand other modifications that may be made that are contemplatedwithin the scope of other embodiments. Although process embodiments maybe described in a particular order, various other process embodimentsmay be performed in any logical order and may include fewer or moreoperations than what is described herein.

A metal gate structure may include a gate dielectric layer, a barrierlayer over the gate dielectric layer, a work function metal layer overthe barrier layer, and a gate metal fill over the work function metallayer. Some embodiments described herein are directed to providing adevice, and a method of forming the same, in which the device includes ametal silicate layer. The metal silicate layer is formed throughpassivation or forming a silicon passivation layer over the barrierlayer using a silicon precursor and through annealing the metal gatestructure. In certain embodiments, the metal gate structure exhibits anincrease in dielectric value along with a boost in device performance.

FIG. 1 depicts an exemplary flow diagram of a process 8 performed toform a high-k metal gate structure, such as described with respect toFIG. 2 to FIG. 15. FIG. 2 is a schematic perspective view and FIG. 3 toFIG. 15 are schematic cross-sectional views of a portion of thesubstrate corresponding to various stages of the process 8 in accordancewith some embodiments. The process 8 may be utilized to form anysuitable structures, including the structures depicted in FIG. 2 to FIG.15 or in other applicable semiconductor structures.

As shown in FIG. 2, the structure includes a substrate 20. The substrate20 can be or include a bulk semiconductor substrate, asemiconductor-on-insulator (SOI) substrate, or another substrate. Thesemiconductor material of the substrate 20 can include or be a materialselected from at least one of silicon (e.g., crystalline silicon likeSi<100> or Si<111>), silicon germanium, germanium, gallium arsenide, oranother semiconductor material. The semiconductor material may be dopedor undoped, such as with a p-type or an n-type dopant. In someembodiments wherein a SOI structure is utilized for the substrate 20,the substrate 20 may include semiconductor material disposed on aninsulator layer, which may be a buried insulator disposed in asemiconductor substrate, or which may be a glass or sapphire substrate.In certain embodiments, the substrate 20 is a silicon wafer. Forexample, the substrate 20 may be a round substrate having a 150 mmdiameter, 200 mm diameter, a 300 mm diameter, a 450 mm diameter, orother diameters. In other embodiments, the substrate 20 may be anyparticular size, shape, or materials. For example, the substrate 20 mayalso be any polygonal, square, rectangular, curved, or otherwisenon-circular workpiece.

The structure includes one or more semiconductor fins, referred toherein as fin structures 22. Each fin structure 22 provides an activeregion where one or more electronic circuits are formed. The finstructures 22 are fabricated using suitable processes including masking,photolithography, and/or etch processes. An etch process forms recesses23 into the substrate, leaving an extending fin, such as the finstructures 22. The recesses 23 may be etched using reactive ion etch(RIE) and/or other suitable processes. Numerous other embodiments ofmethods to form a fin structure on a substrate may be utilized. Forexample, a fin structure can be epitaxially grown in trenches and canhave a general structure similar to what is shown in the figures.

In certain embodiments, the fin structures 22 comprise silicon materialsor another elementary semiconductor, such as germanium, or a compoundsemiconductor including silicon carbide, gallium arsenic, galliumphosphide, indium phosphide, indium arsenide, and/or indium antimonide.The fin structures 22 may also be an alloy semiconductor including SiGe,GaAsP, AlInAs, AlGaAs, GalnAs, GaInP, GaInAsP, or a combination thereof.The fin structures 22 may be doped using n-type and/or p-type dopants asneeded.

The recesses 23 may be filled with a dielectric material that is etchedback to form isolation structures 24. Other fabrication processes forthe isolation structures 24 and/or the fin structure 22 are possible.The isolation structures 24 may isolate some regions of the substrate20, e.g., active areas in the fin structures 22. In certain embodiments,the isolation structures 24 may be shallow trench isolation (STI)structures and/or other suitable isolation structures. The STIstructures may be formed of silicon oxide, silicon nitride, siliconoxynitride, fluoride-doped silicate glass (FSG), a low-k dielectricmaterial, and/or other suitable insulating material. The STI structuresmay include a multi-layer structure, for example, having one or morelayers.

A dummy gate structure 28 is formed over the fin structures 22. In theexample depicted in FIG. 2, the dummy gate structure 28 includes aninterfacial dielectric layer 30, a dummy gate layer 32, and a hardmasklayer 34. The dummy gate structure 28 may further include a cappinglayer and/or other suitable layers. The various layers in the dummy gatestructure 28 may be formed by suitable deposition processes andpatterned by suitable photolithography and etching processes. The dummygate structure 28 engages the fin structures 22 on the sides and top ofthe fin structure 22. The term “dummy”, as used here, refers to asacrificial structure which will be removed in a later stage and will bereplaced with another structure, such as a high-k gate dielectric layerand a metal gate in a replacement gate process. The replacement gateprocess refers to manufacturing a gate structure at a later stage of theoverall gate manufacturing process.

The interfacial dielectric layer 30 can be a dielectric oxide layer. Forexample, the dielectric oxide layer may be formed by chemical oxidation,thermal oxidation, atomic layer deposition (ALD), chemical vapordeposition (CVD), and/or other suitable methods. The dummy gate layer 32may be a poly-silicon layer or other suitable layers. For example, thedummy gate layer 32 may be formed by suitable deposition processes suchas low-pressure CVD (LPCVD) and plasma-enhanced CVD (PECVD). Thehardmask layer 34 may be any material suitable to pattern the dummy gatestructure 28 with desired features/dimensions on the substrate.

In certain embodiments, the various layers of the dummy gate structure28 are first deposited as blanket layers. The blanket layers arepatterned through a process including photolithography and etchingprocesses, removing portions of the blanket layers and keeping theremaining portions over the isolation structures 24 and the finstructures 22 to form the dummy gate structure 28.

In certain embodiments, the structure may be in a p-type device regionfor forming one or more p-type devices, or an n-type device region forforming one or more n-type devices. The structure may be included in anintegrated circuit such as logic devices, memory devices, and/or otherICs.

In certain embodiments, a spacer feature 36 is formed on sidewalls ofthe dummy gate structure 28, as shown in FIG. 3. FIG. 3 illustrates across-sectional view along the line A-A through one of the finstructures 22 of FIG. 2. The spacer feature 36 includes a materialdifferent from the material(s) for the dummy gate structure 28. Thespacer feature 36 includes a dielectric material, such as siliconnitride or silicon oxynitride. The spacer feature 36 may be a singlelayer or multiple layers. In certain embodiments, after the dummy gatestructure 28 is formed, one or more spacer layers are formed byconformally depositing spacer materials over the structure. Ananisotropic etching process is performed to remove portions of thespacer layers to form the spacer feature 36, as depicted in FIG. 3.

After the spacer feature 36 is formed, one or more epitaxial growthprocesses may be performed to grow epitaxy source/drain regions 42. Theepitaxy source/drain regions 42 may be formed in recesses of the finstructure 22 or over non-recessed fin structures (not shown). Theepitaxial growth process may in-situ dope the epitaxy source/drainregions with a p-type dopant for forming a p-type device or an n-typedopant for forming an n-type device.

Subsequently, an interlayer dielectric (ILD) 52 is formed over thesubstrate 20 and over the spacer feature 36. In certain embodiments, thestructure may further include a contact etch stop layer 50 underneaththe ILD 52 and over the spacer feature 36. The ILD 52 may includematerials such as a silicon oxide (e.g., such as a silicon oxide formedby tetraethylorthosilicate (TEOS)), un-doped silicate glass, dopedsilicon oxide such as borophosphosilicate glass (BPSG), fluoride-dopedsilicate glass (FSG), phosphosilicate glass (PSG), boron doped siliconglass (BSG), and/or other suitable dielectric materials. The ILD 52 maybe deposited by a PECVD process, high density plasma CVD (HDPCVD)process, or other suitable deposition processes. The ILD 52 is formed toat least fill the recesses 23 between neighboring dummy gate structures28.

A chemical mechanical planarization (CMP) process is performed toplanarize the ILD 52 and the spacer feature 36 to expose the dummy gatestructure 28, and, once exposed, the dummy gate structure 28 is removedfrom the substrate 20 to define a gate trench 54 in the ILD 52 as shownin FIG. 4. The gate trench 54 exposes a surface of the isolationstructures 24 (not visible in the cross-section of FIG. 4) and surfacesof the fin structure 22. The dummy gate structure 28 may be removedusing an etch process, such as a dry (plasma) etch, a wet etch, and/orother suitable etch processes. For example, a dry etching process mayuse chlorine-containing gases, fluorine-containing gases, other etchinggases, or a combination thereof. The wet etching solutions may includeHF (hydrofluoric acid), TMAH (tetramethylammonium hydroxide), othersuitable wet etching solutions, or combinations thereof.

At operation 10 of the process 8 of FIG. 1, an interfacial layer 60 isformed over the gate trench 54 as shown in FIG. 5. In certainembodiments, the interfacial layer 60 may include a dielectric materialsuch as a silicon oxide layer (SiO₂), a silicon oxynitride (SiON) layer,and the like. The interfacial layer 60 may be formed by chemicaloxidation, thermal oxidation, ALD, CVD, and/or other suitable processes.The interfacial layer 60 maybe formed to an initial thickness in a rangefrom about 5 Å to about 10 Å. Although the interfacial layer 60 asdepicted in FIG. 5 as being formed over the fin structure 22, theinterfacial layer 60 may be also formed along sidewalls of the spacerfeatures 36.

At operation 11 of the process 8 of FIG. 1, a high-k gate dielectriclayer 62 is deposited over the interfacial layer 60 as shown in FIG. 6.The high-k gate dielectric layer 62 comprises a metal oxide materialhaving a high-k dielectric constant. For example, the high-k gatedielectric layer 62 may comprise hafnium oxide (HfO_(x)), AlO_(x),lanthanum oxide (LaO_(x)), TiO_(x), HfZr_(x)O_(y), HfSi_(x)O_(y),ZrO_(x), ZrSi_(x)O_(y), TaO_(x), YO_(x), SrTi_(x)O_(y), BaTi_(x)O_(y)(BTO), BaZr_(x)O_(y), HfZr_(x)O_(y), HfZr_(x)O_(y)N_(z), HfLa_(x)O_(y),HfSi_(x)O_(y), HfSi_(x)O_(y)N_(z), LaSi_(x)O_(y), AlSi_(x)O_(y),HfTa_(x)O_(y), HfTi_(x)O_(y), (Ba,Sr)Ti_(x)O_(y) (BST), combinationsthereof, or other suitable material. In certain embodiments, the high-kgate dielectric layer 62 comprises LaO_(x), LaSi_(x)O_(y),HfLa_(x)O_(y), or combinations thereof. The high-k gate dielectriclayers 62 may be formed by ALD, CVD, and/or other suitable methods. Inother embodiments, the high-k gate dielectric layer 62 may be directlyformed on the substrate 20 (e.g., on the fin structure 22) when theinterfacial layer 60 is not present.

At operation 12 of the process 8 of FIG. 1, a barrier layer 64 isdeposited over the high-k gate dielectric layer 62 as shown in FIG. 7.The barrier layer 64 comprises titanium nitride (TiN), tantalum nitride(TaN), multiple layers thereof, or other suitable materials. In certainembodiments, the barrier layer 64 may have a thickness in a range fromabout 5 angstroms to about 20 angstroms. The barrier layer 64 may beconformally deposited, such as by CVD processes, including PECVD,metal-organic CVD (MOCVD), ALD, cyclic deposition, or other suitabledeposition processes.

In certain embodiments, the barrier layer 64 may be a TiN layerdeposited by cyclic deposition, such as by ALD. In cyclic deposition,multiple cycles of precursors are flowed to a surface of a substrate todeposit a layer thereover. Each cycle includes providing a pulse of atitanium precursor, such as titanium chloride (TiCl₄), and a pulse of anitrogen precursor, such an ammonia gas (NH₃), to form TiN. In certainembodiments, the titanium precursor is provided at a flow rate in arange from about 50 sccm to about 150 sccm. In certain embodiments, thenitrogen precursor is provided at a flow rate in a range from about 50sccm to about 150 sccm. In certain embodiments, the cyclic deposition isconducted at a pressure in a range from about 1 torr to about 15 torr,such as in a range from about 4 torr to about 8 torr.

A pulse of a purge gas between the pulses of the titanium precursor andthe nitrogen precursor may help to remove excess titanium precursor andnitrogen precursor on the surface of the substrate to help providecontrolled growth. Instead of a pulse of a purge gas, a pump down ofsufficient duration between the pulse of the titanium precursor and thepulse of the nitrogen precursor may be used to help to remove excesstitanium precursor and nitrogen precursor on the surface of thesubstrate to help provide controlled growth. In certain embodiments, aplasma may also be provided. For example, the pulse of a nitrogenprecursor may be provided as a plasma. In certain embodiments, eachcycle may form about a monolayer or atomic layer of titanium nitride. Inother embodiments, each cycle may form less than a monolayer due topartial adsorption or partial reaction of the titanium precursor and thenitrogen precursor. In other embodiments, each cycle may form more thana monolayer due to only partial or no removal of excess titaniumprecursor and nitrogen precursor on the surface of the substrate.

In other embodiments, other titanium precursors may be used instead ofor in combination with TiCl₄, such as titanium iodide (TiI₄), titaniumbromide (TiBr₄), tetrakis (dimethylamido) titanium (TDMAT), tetrakis(diethylamido) titanium (TDEAT), tetrakis (diethylamido) titanium(TDEAT), and other suitable titanium precursors. In other embodiments,other nitrogen precursors may be used instead of or in combination withammonia, such as hydrazine (N₂H₄), monomethyl hydrazine (CH₃N₂H₃),dimethyl hydrazine (C₂H₆N₂H₂), t-butylhydrazine (C₄H₉N₂H₃),phenylhydrazine (C₆H₅N₂H₃), 2,2′-azoisobutane ((CH₃)₆C₂N₂), ethylazide(C₂H₅N₃), nitrogen (N₂), other suitable nitrogen precursors, andcombinations thereof.

At operation 13 of the process 8 of FIG. 1, a silicon passivation layer66 is deposited over the barrier layer 64 as shown in FIG. 8. In certainembodiments, the silicon passivation layer 66 comprises of silicon orhydrogenated silicon. The silicon passivation layer 66 may be depositedby soaking the structure with a silicon precursor to deposit silicon bythermal decomposition, plasma decomposition, or other suitabledeposition processes. The silicon precursor may be silane, disilane,trisilane, combinations thereof, or other suitable silicon precursors.In certain embodiments, the silicon passivation layer 66 is deposited toa thickness in a range from about 0.5 Å to about 15 Å, such as in arange from about 3 Å and about 10 Å. The silicon passivation layer 66helps to protect the barrier layer 64. If the silicon passivation layer66 is too thin, then oxygen may diffuse through the passivation layer 66to the layers below, such as the barrier layer 64, the gate dielectriclayer 62, and/or the interfacial layer 60. If oxygen diffuses into theinterfacial layer 60, the properties of the structure may be adverselyimpacted, such as altering a threshold voltage Vt of a transistor thatis formed. If silicon passivation layer 66 is too thick, then thesilicon passivation layer 66 may adversely impact the nitrogen precursortreatment of operation 14 by inhibiting the penetration of nitrogen tothe layers below.

In certain embodiments, the silicon precursor is provided at a flow ratein a range from about 300 sccm to about 500 sccm. In some embodiments,an additional process gas and/or carrier gas may also be provided, suchas hydrogen gas. In certain embodiments, the soak is performed at atemperature in a range from about 400° C. to about 600° C. If atemperature lower than 400° C. is used during the silicon precursorsoak, the silicon precursor may not sufficiently decompose to form asilicon layer over the barrier layer 64. For example, the formation of asilicon passivation layer of silicon or hydrogenated silicon may form bythe following reaction in formula (I):SiH₄(g)→Si(s)+2H₂(g)  (I)If a temperature higher than 600° C. is used during the siliconprecursor soak, it may be difficult to control the deposition rate ofthe silicon material. In certain embodiments, a silicon precursor isprovided at a flow rate for a duration in a range from about 2 minutesto about 10 minutes.

At operation 14 of the process 8 of FIG. 1, the structure is treatedwith nitrogen, referred to herein as a nitrogen treatment 67, as shownin FIG. 9. The nitrogen treatment 67 comprises flowing a nitrogenprecursor to the structure. The nitrogen precursor may be ammonia,hydrazine (N₂H₄), nitrogen gas, other suitable nitrogen-containing andoxygen-free precursors, and combinations thereof. In certainembodiments, the nitrogen precursor is provided at a flow rate in arange from about 5 slm to about 15 slm, such as in a range from about 7slm to about 11 slm. In certain embodiments, the nitrogen treatment is apost-metal anneal (PMA) performed at a temperature in a range from about700° C. to about 1,000° C. In certain embodiments, the nitrogentreatment is provided in a two-operation post-metal anneal process. Incertain aspects, a post metal anneal process performed in two or moreoperations reduces damage to the semiconductor devices of thesemiconductor substrate due to overshooting of the intended annealtemperature. For example, a first operation comprises a first anneal ata temperature in a range from about 700° C. to about 800° C. and asecond operation comprises a second anneal at a temperature higher thanthe first anneal, such as a second anneal at a temperature in a rangefrom about 850° C. to about 930° C. In another example, the firstoperation comprises a first anneal at a temperature in a range fromabout 700° C. to about 800° C. at a pressure in a range from about 40torr to about 50 torr, and the second operation comprises a secondanneal at a temperature in a range from about 850° C. to about 930° C.at a pressure in a range from about 1 torr to about 10 torr.

In certain aspects, the nitrogen treatment 67 is conducted at a certaintemperature and certain pressure to provide a thermal nitridation of thestructure to cause the nitrogen to penetrate into the barrier layer 64,the gate dielectric layer 62, and/or the interfacial layer 60. If thetemperature and/or the pressure of the nitrogen treatment is too low, aninsufficient amount of nitrogen may dissociate from the nitrogenprecursor to penetrate into the layers of the structure. If thetemperature of the nitrogen treatment is too high, the structure may bedamaged. If the pressure of the nitrogen treatment is too high, thenitrogen precursor may be wasted due to low residence time to thestructure. In other embodiments, a plasma nitridation of the structurein which a nitrogen plasma is provided to the structure may be performedalternatively or in combination with a thermal nitridation.

In certain embodiments, the nitrogen treatment 67 passivates the barrierlayer 64, the high-k gate dielectric layer 62, and/or the interfaciallayer 60. Dangling bonds and charge trapping sites may be present withinthe barrier layer 64, the high-k gate dielectric layer 62, and/or theinterfacial layer 60 and may be present at the interfaces between thebarrier layer 64, the high-k gate dielectric layer 62, and/or theinterfacial layer 60. Introduction of nitrogen from the nitrogentreatment 67 can passivate the dangling bonds and eliminate some of thecharge trapping sites that otherwise would exist. In certainembodiments, the nitrogen treatment 67 drives in nitrogen from thenitrogen precursor and/or from the barrier layer 64 comprising a metalnitride, such as titanium nitride, into the high-k gate dielectric layer62 and into the interfacial layer 60. In certain embodiments, thenitrogen treatment 67 drives in nitrogen from the nitrogen precursorinto the barrier layer 64 comprising a metal nitride, such as titaniumnitride, and densifies the barrier layer 64 to enhance the barrierproperties of the barrier layer 64.

In certain embodiments, operations 12, 13, and 14 are performed withinthe same integrated process system without exposing the structure to theambient environment or to air. In some embodiments, operation 12 andoperation 13 may be performed in the same processing chamber, or in-situwith one process recipe to perform the operation 12 to deposit thebarrier layer 64 and another process recipe to perform the operation 13to deposit the silicon passivation layer 66. In some embodiments,operation 14 may be performed in a rapid thermal processing (RTP)chamber so that the high temperature of operation 14 may be quicklyachieved. In other embodiments, the operation 14 of a nitrogen treatmentof the structure is performed first, and then the operation 13 isperformed to deposit the silicon passivation layer 66.

At operation 15 of the process 8 of FIG. 1, a capping layer 68 isdeposited over the silicon passivation layer 66 as shown in FIG. 10. Thecapping layer 68 may comprise silicon, other suitable materials, orcombinations. In certain embodiments, the capping layer 68 comprisessilicon or hydrogenated silicon is deposited by using a siliconprecursor, such as silane, disilane, or combinations thereof, by thermaldecomposition, plasma decomposition, or other suitable depositionprocesses. The formation of a capping layer 68 of silicon orhydrogenated silicon may form by formula (I) above. In certainembodiments, the capping layer 68 is formed to a thickness in a rangefrom about 20 Å to about 40 Å. In certain embodiments, the capping layer68 provides additional protection of the barrier layer 64 in addition tothe protection from the silicon passivation layer 66 from exposure tothe ambient environment or to air.

At operation 16 of the process 8 of FIG. 1, an anneal 69, such as a postcapping layer anneal, of the structure of FIG. 10 is performed as shownin FIG. 11. In certain embodiments, the anneal is performed at atemperature in a range from about 800° C. to about 1,000° C. The anneal69 may be performed in an RTP chamber. In certain embodiments, theanneal 69 causes weakly bonded oxygen in the interfacial layer 60, thehigh-k gate dielectric layer 62, and/or the barrier layer 64 to bescavenged and absorbed by the silicon passivation layer 66, and/or thecapping layer 68. The oxygen diffuses out of the interfacial layer 60,the high-k gate dielectric layer 62, and/or the barrier layer 64 toreact with the silicon passivation layer 66 and/or the capping layer 68.In certain embodiments, the anneal 69 causes the silicon passivationlayer 66 and/or the capping layer 68 to absorb oxygen from theinterfacial layer 60 reducing the thickness of the interfacial layer.The thickness of the interfacial layer 60 may be reduced by more than30% from an initial thickness. A thinner interfacial layer 60 helps toimprove the transistor characteristics. In certain embodiments, athinner interfacial layer 60 in combination with the high-k gatedielectric layer 62 provides better threshold voltage V_(t) performanceof a high-k metal gate structure.

During the anneal 69 of operation 16 (and/or during the thermalnitridation at operation 14), metal from the high-k gate dielectriclayer 62 and oxygen from the interfacial layer 60 and/or the high-k gatedielectric layer 62 diffuse to the silicon passivation layer 66 forminga metal silicate layer 70 at the interface of the silicon passivationlayer 66 and the barrier layer 64. For example, for a high-k gatedielectric layer 62 comprising LaO_(x) and/or LaSi_(x)O_(y), thediffused lanthanum reacts with the silicon of the silicon passivationlayer 66 and with the diffused oxygen at the silicon passivation layer66 to form a lanthanum silicate (LaSi_(x)O_(y)). In another example, fora high-k gate dielectric layer 62 comprising HfLa_(x)O_(y), the diffusedlanthanum and diffused hafnium react with the silicon of the siliconpassivation layer 66 and with the diffused oxygen at the siliconpassivation layer 66 to form a hafnium lanthanum silicate(HfLa_(x)Si_(y)O_(z)). In certain embodiments, the metal silicate layer70 comprises a high-k dielectric material. The high-k gate dielectriclayer 62 and metal silicate layer 70 comprising a high-k dielectricmaterial act as a gate dielectric between a metal fill layer 76 (asshown in FIG. 15) and the fin structure 22 to help reduce leakagecurrent and to boost device performance.

At operation 17 of the process 8 of FIG. 1, the capping layer 68 isremoved as shown in FIG. 12. The capping layer may be removed by dryetching (such as plasma etching or reactive ion etching), wet etching,or other etching processes. For example, the etch process may be anisotropic etch process. In certain embodiments, the silicon passivationlayer 66 is also removed at operation 17. For example, when the cappinglayer 68 comprises silicon, the silicon passivation layer 66 is removedat operation 17 since the capping layer 68 and the silicon passivationboth comprise silicon. After operation 17, the metal silicate layer 70remains over the barrier layer 64.

At operation 18 of the process 8 of FIG. 1, one or more work functionmetal layers 72 are deposited over the metal silicate layer 70 as shownin FIG. 13. One or more work function metal layers 72 are chosen to tunethe work function value of the FinFET devices so that a desiredthreshold voltage Vt can be achieved in the transistor that is formed.Examples of a work function metal layer 72 for a gate structure forn-type FinFET devices include Ti, Ag, TaAl, TaAlC, TiAlN, TaC, TaCN,TaSiN, Mn, Zr, other suitable work function materials, or combinationsthereof. Examples of a work function metal layer 72 for p-type FinFETdevices include TiN, TaN, Ru, Mo, Al, WN, ZrSi₂, MoSi₂, TaSi₂, NiSi₂,WN, other suitable work function materials, or combinations thereof. Thework function metal layer 72 may have a thickness in a range from about20 angstroms to about 100 angstroms. The work function metal layer 72may be conformally deposited, such as by CVD processes, including PECVD,MOCVD, ALD, cyclic deposition, or other suitable deposition processes.

At operation 19 of the process 8 of FIG. 1, a metal fill layer 76 isdeposited over the work function metal layer 72 as show in FIG. 14. Incertain embodiments, the metal fill layer 76 may comprise tungsten,cobalt, aluminum, ruthenium, copper, other suitable metals, multi-layersthereof, a combination thereof, or the like. The metal fill layer 76 maybe deposited by a suitable process, such as CVD, physical vapordeposition (PVD), sputtering, ALD, PECVD, plating, or other depositionprocesses.

The structure may be further processed as shown in FIG. 15. The high-kgate dielectric layer 62, the barrier layer 64, the metal silicate layer70, the work function metal layer 72, and the metal fill layer 76 may beplanarized, such as by a CMP process or another suitable planarizationprocess. An ILD 80 may be deposited over the planarized structure by adeposition process, such as CVD, PVD, ALD, HDPCVD, MOCVD, or PECVD. Forexample, the ILD 80 may be silicon oxide, silicon nitride, siliconoxynitride, phospho-silicate glass (PSG), boro-silicate glass (BSG),boron-doped phospho-silicate glass (BPSG), or other dielectric layers.The ILD 80 may be patterned to form openings that are filled with metal,such as copper, tungsten, or other suitable metals, to form contacts 82contacting the source/drain regions 42. The contacts 82 may be depositedby PVD, electrochemical deposition, CVD, combinations thereof, or othersuitable deposition processes.

FIG. 16 is a graph 200 of an atomic percent content in a high-k metalgate structure, such as the structure of FIG. 15, in accordance withsome embodiments. The high-k metal gate structure includes a interfaciallayer 60 comprising silicon oxide, a high-k gate dielectric layer 62comprising HfLa_(x)O_(y), a barrier layer 64 comprising titaniumnitride, and a metal silicate layer 70 comprising HfLa_(x)Si_(y)O_(z)For ease of illustration, the atomic content of silicon and nitrogen isomitted from the graph 200. As shown in the graph 200, lanthanum andhafnium have diffused from the high-k gate dielectric layer 62 to formthe metal silicate layer 70. The peak concentration of lanthanum andhafnium is in the HfLa_(x)O_(y) high-k gate dielectric layer 62 incomparison to the silicon oxide interfacial layer 60, the titaniumnitride barrier layer 64, or the HfLa_(x)Si_(y)O_(z) metal silicatelayer 70. Oxygen from the silicon oxide interfacial layer 60 and/or theHfLa_(x)O_(y) high-k gate dielectric layer 62 has diffused to form theHfLa_(x)Si_(y)O_(z) metal silicate layer 70 as well as forming titaniumoxynitride within the titanium nitride barrier layer 64. In theembodiments as shown in the graph 200, the HfLa_(x)O_(y) high-k gatedielectric layer 62 remains oxygen-rich. If the high-k gate dielectriclayer 62 is not oxygen-rich than the dielectric constant of the high-kgate dielectric would be adversely lower. The oxygen content of theHfLa_(x)O_(y) high-k gate dielectric layer 62 is higher than the oxygencontent of the silicon oxide interfacial layer 60, the titanium nitridebarrier layer 64, or the HfLa_(x)Si_(y)O_(z) metal silicate layer 70.

In certain embodiments, a high-k metal gate structure comprises a high-kgate dielectric layer, a barrier layer over the high-k gate dielectriclayer, a metal silicate layer over the barrier layer, a work functionmetal layer over the metal silicate layer, and a gate electrode over thework function metal layer. The metal silicate layer is formed throughpassivation or forming a silicon passivation layer over the barrierlayer using a silicon precursor and through annealing of the metal gatestructure through a post-metal anneal (e.g., in a thermal nitridation)after forming the barrier layer and/or a post capping layer anneal. Incertain embodiments, the metal gate structure exhibits an increase indielectric value along with a boost in device performance.

An embodiment is a method of semiconductor processing. The methodincludes depositing a high-k gate dielectric layer over a semiconductorfin. A barrier layer is deposited over the high-k gate dielectric layer.A silicon passivation layer is deposited over the barrier layer. Anitrogen treatment is performed on the silicon passivation layer. Acapping layer is deposited over the silicon passivation layer. Thecapping layer is annealed.

Another embodiment is a device structure. The device structure includesa high-k gate dielectric layer over a semiconductor fin. A barrier layeris over the high-k gate dielectric layer. A metal silicate layer is overthe barrier layer. A work function metal layer is over the metalsilicate layer. A metal fill layer is over the work-function metallayer.

Yet another embodiment is another method of semiconductor processing.The method includes depositing a high-k gate dielectric layer comprisinga metal oxide over a semiconductor fin. A barrier layer is depositedover the high-k gate dielectric layer. A silicon passivation layer isdeposited over the barrier layer. The barrier layer and the siliconpassivation layer are deposited in situ. A nitrogen treatment isperformed on the silicon passivation layer. A capping layer is depositedover the silicon passivation layer. A metal silicate layer is formed byannealing the silicon passivation layer to diffuse a metal from themetal oxide of the high-k gate dielectric layer.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method of semiconductor processing, the methodcomprising: depositing a high-k gate dielectric layer over asemiconductor fin; depositing a barrier layer over the high-k gatedielectric layer; depositing a silicon passivation layer over thebarrier layer; performing a nitrogen treatment on the siliconpassivation layer; depositing a capping layer over the siliconpassivation layer; and annealing the capping layer.
 2. The method ofclaim 1, further comprising forming an interfacial layer over thesemiconductor fin, wherein the high-k gate dielectric layer is formedover the interfacial layer.
 3. The method of claim 2, wherein thenitrogen treatment drives nitrogen into the high-k gate dielectric layerto passivate the high-k gate dielectric layer and the interfacial layer.4. The method of claim 1, wherein the depositing the barrier layer, thedepositing the silicon passivation layer, and the performing thenitrogen treatment is performed without exposing the barrier layer orthe silicon passivation layer to air.
 5. The method of claim 4, whereinthe barrier layer is deposited and the silicon passivation layer isdeposited in the same chamber.
 6. The method of claim 1, wherein thesilicon passivation layer is deposited to a thickness in a range fromabout 0.5 Å to about 10 Å.
 7. The method of claim 1, wherein theannealing causes the silicon passivation layer and the capping layer toabsorb oxygen.
 8. A method of semiconductor processing, the methodcomprising: depositing a high-k gate dielectric layer comprising a metaloxide over a semiconductor fin; depositing a barrier layer over thehigh-k gate dielectric layer; depositing a silicon passivation layerover the barrier layer, wherein the barrier layer and the siliconpassivation layer are deposited in situ; performing a nitrogen treatmenton the silicon passivation layer; depositing a capping layer over thesilicon passivation layer; and forming a metal silicate layer byannealing the silicon passivation layer to diffuse a metal from themetal oxide of the high-k gate dielectric layer.
 9. The method of claim8, wherein the barrier layer is deposited by a cyclic deposition. 10.The method of claim 9, wherein the cyclic deposition comprises flowing atitanium precursor at a flow rate in a range from about 50 sccm to about150 sccm, and comprising flowing a nitrogen precursor at a flow rate ina range from about 50 sccm to about 150 sccm.
 11. The method of claim 8,wherein the silicon passivation layer is deposited at a temperature in arange from about 400° C. to about 600° C.
 12. The method of claim 8,wherein the nitrogen treatment comprises a thermal nitridation conductedat a temperature in a range from about 700° C. to about 1,000° C. 13.The method of claim 12, wherein thermal nitridation comprises a firstanneal at a first temperature in a first range from about 700° C. toabout 800° C., and a second anneal at a second temperature in a secondrange from about 850° C. to about 930° C.
 14. A method of semiconductorprocessing, the method comprising: depositing a metal oxide layer over asemiconductor fin; depositing a barrier layer over the metal oxidelayer; depositing a silicon-containing layer over the barrier layer;performing a nitridation process to introduce nitrogen into the barrierlayer; depositing a capping layer over the silicon-containing layer;after depositing the capping layer, annealing the semiconductor fin withthe metal oxide layer, the barrier layer, the silicon-containing layer,and the capping layer, the annealing forming a metal silicate layer; andremoving the capping layer.
 15. The method of claim 14, wherein thebarrier layer and the silicon-containing layer are deposited in situ.16. The method of claim 14, wherein the nitridation process introducesnitrogen into the metal oxide layer.
 17. The method of claim 14, furthercomprising removing remains of the silicon-containing layer.
 18. Themethod of claim 14, wherein the silicon-containing layer consistsessentially of silicon or hydrogenated silicon.
 19. The method of claim14, wherein the nitridation process comprises a thermal nitridationprocess.
 20. The method of claim 14, wherein the nitridation processcomprises a plasma nitridation process.